Measuring dispensing sheet for germicides and process of forming same



United States Patent MEASURING DISPENSING SHEET FOR GERMI- CIDES ANDPROCESS OF FORMING SAlVlE Louis L. Lerner, Chicago, 111., assignor toPhil Kalech, Jack I. Le Vant, and Nat Kalech, a copartnership, doingbusiness as Phil Kalech Company, Chicago, Ill.

No Drawing. Application October 10, 1950, Serial No. 189,486

6 Claims. (Cl. 167-84) The present invention relates to dispensingmeasured quantities of germicidal agents in preparing germicidalsolutions, and in particular it also relates to a measuring germicidedispenser suitable additionally as an appllcator for a germicidalsolution produced therefrom.

Germicidal solutions are required to be used by health authorities inmany places, for example, in dairles, res-. taurants, hotels and otherindustries, particularly those dealing with food. For such uses, theauthorities speclfy solutions of minimum germicidal potency. This isparticularly true in dairies and restaurants. One important use indairies besides treating containers and other equipment, is the use ofsuch solutions to wash the flanks and udders of milk cows.

It is well known that many of the quaternary ammonium salts (hereinafterreferred to as quaternaries or as a quaternary) are water-dispersibleand at moderately low concentrations are highly germicidal in action,and relatively harmless to the human organism. Among the micro-organismsagainst which it has been reported that the quaternaries are efiectiveare:

Eberthella typhosa; staphylococcus aureus; staphylococcus albus;escherichia coli; streptococcus hemolyticus; (streptococcus pyogenes);streptococcus viridans (streptococcus salivarius); streptococcusagalactiae; streptococcus salivarius (strep. viridans); streptococcuspyogenes (strep. hemolyticus); manilia albicans; microsporon lanosum;microsporon audouini; tricophyton iuterdigitale; pseudomonas aeruginosa;achorion schoenleini; proteus vulgaris; bacillus subtilis;epidermophyton inguinale; sarcina lutea; actinomyces gedanensis; andsaccharomyces cerevisiae.

In those places where public health inspection is common, the inspectorusually checks upon the kind of germicide used, the germicidal potencyof the solutions used, the potency being determined by the concentrationof the germicide if other agents are not present. Standards are so setthat maintenance of the specified minimum of concentration of materialconsisting of the germjcide assures the result sought. Usually in suchplaces it is the hired help which is obligated to prepare and use thesterilizing solution in the sanitizing practices. To assure adequatecompliance with such duty, it is very important to make it simple andeasy, as well as a desirable act, to do the expected work properly. Itis one of the objectives of the present invention to provide aninstrumentality leading to simple and easy performance of the tasks andinviting proper conduct thereof in a manner to satisfy inspectionauthorities.

It is not suficiently practicable to provide a concentrated supply ofquaternary material with instructions for measuring and dispersing itinto a prescribed quantity of water to prepare it for proper use. Thepresent invention overcomes these practical problems and offers newadvantages as well.

The present invention is based upon finding that certain kinds of sheetmaterial may be treated with a quaternary solution under controlledconditions, so that equal areas of the sheet will yield to water likeamounts of the quaternary. It is also based upon finding that thequaternary is held by surface adsorption or substantivity on sheets witha smooth face, and by like action plus capillarity in certain othersheets. In sheets lacking capillarity, the amount held is small andcontrollable, 3

whereas in sheets having capillarity the amount held is 2,702,780Patented Feb. 22, 1955 correspondingly increased. In the presentinvention, where sheets with capillarity are preferred, a sheet ofcontrolled structure is employed whereby the capillarity issubstantially uniform and subject to control for regulating theuniformity of content of quaternary.

It is therefore the general object of the present invention to providean adequate carrier sheet, and to treat the sheet with water-dispersiblegermicidal quaternary compound for uniformity of content with respect topieces having the same area.

It is an object of the invention to provide such a carrying sheet withstrength-giving fibers to impart capillarity.

It is another object of the invention to provide such a carrying sheethaving an appreciable wet strength whereby it may be used as anapplicator in using the solution prepared therefrom.

Various other and ancillary objects and advantages of the invention willappear from the following description and explanation of the inventionand its advantages.

Taking the dairy industry as an example, it may be stated that it is amust that a milk cow be washed before milking, and in that matter thepractice is so well established that hired help does not neglect it.However, if left to his own devices, the dairy helper may neglect toprepare any or a proper germicidal solution for such washing, and thusendanger the sanitary quality of the milk. In washing, a cloth or thelike must be used, and naturally a fresh and clean cloth is more likelyto be selected by the helper than an old and used one. Also, it iseasier to discard the cloth after milking than to take the trouble toprepare and preserve it for use again at the following milking. Bytaking advantage of these natural human tendencies, the presentinvention practically assures the proper attention to duty by the dairyworker for legal compliance in the washing of milk cows. The samefactors apply in other industries, as will be readily appreciated.

Accordingly, by providing a sheet cut'to size for adding to apredetermined volume of water, one may readily prepare a propersterilizing solution and at the same time, in the preferred practice ofthe present invention, the dispensing medium becomes an applicator orwash cloth, where such is desired, in applying the solution, as forexample, in washing the flanks and udders of the cow.

At first blush it appears logical to impregnate a piece of ordinaryabsorbent paper to provide a carrier sheet of quaternary, to besubdivided as suggested for immersion in water in preparing asterilizing solution. Also, where an applicator sheet or wash cloth isdesired for using the solution, it appears logical to impregnate and drya woven cloth as the carrier sheet. But in doing this, it has been foundthat impregnation is not uniform, and one unit-area piece of theimpregnated paper or cloth differs in available content of quaternaryfrom another and like unit-area piece.

There is in commerce a well-known non-woven cloth made in continuoussheet form and well controlled as to uniformity in structure, consistingof combed cotton or other fibers extending generally in one directionand coated, and bonded and connected into a wet-strength sheet byregenerated cellulose. In making such a nonwoven fabric, a continuousweb of combed cotton or other fibers extending generally in the samedirection is subjected to contact by wet roll or by immersion with asolution of cellulose xanthate (otherwise known as viscose) so as to wetthe fibers therewith and to load interfiber spaces with the thickviscose solution. The Wetted web is then subjected to the action of aregenerating bath, usually acidic in character, to convert the cellulosexanthate content thereof back to cellulose in the form of awater-insoluble hydrophilic gel as a coat on fibers, as an inter-fiberbond, and as thin webs connecting parts of some fibers to parts of otherfibers. The residual chemical is then washed out and the sheet is driedto provide a finished article. Such sheet material is made in variousweights and thicknesses which are standard articles of commerce. Theyare made with variable content and being made from cellulose in solutionform as cellulose xanthate, a solution of cuprammonium cellulose may beapplied and regenerated in a well known manner.

I have discovered that such a cellulose bonded and treated cotton fibersheet either in its initial wet or in its dry state may be passedthrough an aqueous bath of germicidal quaternary, to adsorb and carryaway a controlled quantity of such solution after first draining away orsqueezing out excess liquid in a controlled procedure. The drainedsheet, dried or not, is uniformly over its area a carrier of thequaternary compound.

A study of various sheet materials passed through or immersed in astrong solution of quaternary, drained and dried, has revealed why somesheets are non-uniform carriers and why others are uniform carriers.Uniformity is a practical necessity. If the public is provided with asheet size X suitable for two gallons of water, the public will at onetime or another use half of that sheet for one gallon of water. It istherefore essential that any given area contain the same quantity.

It is known that the surfaces of most materials are so chargedelectrically that cationic surface active materials, of which thesubject quaternaries are examples, are electrostatically depositedthereon in oriented molecular arrangement such as to provide a newsurface which is that of the adsorbed cationic agent. This is amolecular film strongly held against dissolution in water, even thoughthe quaternary is soluble in water. Fabrics are presently madewater-resistant by treatment to deposit such a molecular film ofcationic material.

In the present invention this surface-deposition occurs as soon as anysheet material is subjected to a quaternary solution. Thus, in immersingin a quaternary bath, a material having non-capillary faces, metal foilsand organic films, for example, aluminum foil or cellophane, it isimmaterial what the body is composed of. Only the surface is active, andimmediately the surfaces, whether of aluminum foil or cellophane, becomeidentical in being the surface of oriented molecules of the quaternary.In removing such films from the bath and draining, there is a residualadhering film of the bath which on drying leaves its solid content onthe sheet, uniformly distributed where the draining procedure isuniformly conducted. The stronger the bath, the more the residue.

This is demonstrated by using films of impervious greaseproof glassinepaper, having different thicknesses, and hence proportional capacitiesto absorb water. Pieces of the same size immersed in the same bathabsorb internally weights of water proportional to thickness, but carryequal quantities of residual liquid at the surfaces when draineduniformly; and when dried, have the same carried amount of residualquaternary. The quaternary stops at the surface, but the water of thebath does not. Such glassine sheets have no capillary spaces of size toaccept the quaternary molecule. The carrying capacity for quaternary isdependent on the surface, which is primarily in a dried glassine sheetthe dried residue of hydrated cellulose, or cellulose gel, formed inbeating the stock to provide conventional greaseproof or glassine paper.

Table I shows the results of immersing commercial glassine paper sheetsof 4 x 5 inches in a 20% solution by weight in water of alkyl dimethylbenzyl ammonium chloride wherein the alkyl group varies from 8 to 18carbon atoms, predominating in the lauryl radical (C12H25.), whichquaternary is hereinafter referred to as ADBAC, draining themsubstantially uniformly by simple laboratory technique, and drying.

Table I Gain in Weight Thickness of glassine in inches by addedQuaternary Average The thickness of the sheet is not a factor,demonstrating that the surface, which is devoid of capillary space, isthe controlling factor.

Cellophane sheets, aluminum foil and like non-capillary smooth-facedsheets act likewise, and may be used as carrier sheets for dispensingquaternaries in accordance with the present invention. However, thequantity so available is small relative to practical sizes of thematerial, and the preferred carrier is one having more capacity, notprimarily of smooth surface, but of special capillarity at the surface.In a sheet having such capillarity, the amount of solution held againstdrainage is greater, and hence the retained material is greater.However, the capillarity must be substantially uniform, and not wild.

Examples of wild capillarity are sponge materials, papers and ordinarywoven cloth. By ordinary paper is herein meant a paper sheet which whenexamined under a microscope has voids or capillaries and exhibits abrush-heap appearance. Glassine paper lacks this character, being a filmof dried gel reinforced with the remnants of fibers beaten to providethe gel. Woven cloth has not only capillaries between the threads, butalso within the threads, resulting from twisting so-called smooth-facedor cylindrical fibers, such as cotton, silk, rayon, nylon, into threadform. The capillary capacity is variable over such sheets not only instructure when static, but by physical manipulation of the sheet,especially when wet. Witness a well-drained wet cloth. Squeeze it at oneportion, and liquid is lost. In such materials there is too muchcapillary volume to control it for uniformity with respect to area.

The preferred carrier sheet of the present invention is a compromisebetween the described non-capillary foils and films and sheets havinguncontrollable capillarity, such as ordinary paper and woven cloth. Itis exemplified by the non-woven fabric above described, whether itsfibers are cotton, rayon, silk, nylon, sisal, flax or other fibers. Eventwisted thread of multiple fibers may be used, provided, of course, thatthe thread is sealed to close its capillarity and give it a closedsurface. The non-woven fabric described, or made in a similar way fromother fibers, may be considered as a sheet of fibers each presenting aclosed gel surface of regenerated cellulose, bound fiber to fiber byregenerated cellulose, and in many locations interconnected by thin websor films of regenerated cellulose. Thus, such sheet offers more surfacefor adherence of liquid, and also provides limited and controllablecapillary volume. It has been found that the increase in weight or gaugeof such sheets made of cotten fibers, having a fixed proportion ofregenerated cellulose to cotton, increases the capacity for carriedquaternary. Compared to the glassine sheets, of which the thickness isimmaterial, it shows that the sheet does not act as a flat closedmembrane. However, by increasing the proportion of regeneratedcellulose, the capillarity is lessened, and the sheet approaches and maybecome a fiat closed sheet of cellophane reinforced with imbeddedfibers. Such a closed sheet is useful as an applicator cloth forquaternary carried by it, but because of its lower capacity, relative toa similar type having more capillary volume, it is practically not asuseful, or of as much commercial value, as the preferred kind.

The invention contemplates the production of the nonwoven fabrics asdescribed, with control of capillarity by control of manufacturingprocess. Commercially, this is already a well developed procedure forproviding standard gauge fabrics as to fiber content and regeneratedcellulose content.

The following Table H shows how two non-woven cotton fabrics having from3% to 4 /2% regenerated cellulose content and x gauge (x=grains totalweight per square yard) carry quaternary in proportion to the strengthof bath used, containing in one case ADBAC, and in the other case aquaternary which is herein designated as T. T is alkyl (CsHm to C18H37)dimethyl 3, 4 dichloro benzyl ammonium chlorides and alkenyl (C16 toC20) dimethyl ethyl ammonium bromides, in the ratio of 5 to 1,respectively. In each instance pieces of different size, the weightthereof being proportional to the area, were immersed in the bath,drained in the same way, and dried. The gain in weight is the quaternarymaterial, and is reported as retention in Table II.

The relationship is substantially linear in each case as to retentionand concentration of quaternary, showing that the amount of liquidretained by the sheet in each case is constant, and indicating constancyof surface and capillarity over any selected area, and hence the solidsretention is proportional to the strength of solution.

In production, the non-woven fabric having regenerated cellulose is wetbefore the conventional drying. It may, and preferably should have, forthe present invention, some residual washing alkali (dilute caustic sodasufiices) to give it a pH of 9 or over when containing the quaternary ofthe present invention. The latter is more eflecfive at pH of 9 or over.The sheet, either with its wet undried coagulated and washed regeneratedcellulose of the sheet, or the same sheet dried, with or withoutretained alkali, may be run into the quaternary bath. The dried sheet soused retains somewhat more quaternary than the wet sheet. This isbelieved to be due to the fact that the rewet or rehydrated regeneratedcellulose, having been first dried, does not swell back to the volume ithas before the initial drying. This is believed to result in somewhatmore capillary space in aheh sheets once dried before contact with thequaternary The following results show the constancy of retention in twolarge scale runs, wherein a cotton-web is impregnated with a controlledamount of viscose, then regenerated and washed, and dried, and then runthrough a bath of ADBAC of 21%% strength in Case A and 17% in Case B.Gel content (dry) is 4%.

Case A.--The web of 45 gauge (:2 gauge as manufacturing tolerance) wascut into 2000 pieces each 12 x 12 inches. At random 300 of such sheetswere selected, and divided into 12 groups of 25 sheets each. Each groupwas weighed as a group with results in grams given in Table IH asfollows:

Table 111 Average 135.50 per group Table IV Groups 0! 38 Groups of 33266. 60 Average per group 228. 52

7. Average per sheet 6. 9

4. 66 Average per sq. ft. 4. 6

Case B averages 4.63 grams per sq. ft.

Discussion of Case A and Case B.Considering the different strengths ofbath used, namely 21% and 17%, and Case A as standard, the content of5.42 grams per sq. ft. would indicate that Case B should have 4.3 gramsper sq. ft. for a linear relationship. Actually, 4.66 grams was found.Considering the sheet gauge tolerance of 1:2 in 45, the fabric may varyas much as 4 gauge from maximum to minimum. This is more than thedeviation between contents 4.3 and 4.66.

The invention is not limited to baths containing dispersed materialconsisting of quaternary Other materials may be present. It isbeneficial to have present also a compatible wetting agent, that is, onewhich must be either nonionic or cationic, and hence genericallyreferred to hereinafter as nonanionic. A nonionic wetting agent ispreferred because it is not substantive to the surface of the sheet anddoes not compete with the quaternary for adhesion to the surface of thesheet. A cationic wetting agent does compete and it has been found thatin general a cationic wetting agent should not be present above a ratioof 1 part by weight to two parts of the quaternary. Hence, nonionicwetting agents are the preferred ones, and among them are thosecommercial ones known as Neutronyx 600, Triton X-l00, Ninol 979, andEthofat 242/20. Others are available.

Ninols are trade-marked products of Ninol Laboratories, Chicago,Illinois, made in accordance with Kritchevsky U. S. Patent No.2,089,212. They are condensation products of one mole of aliphaticmonocarboxylic acid with at least two moles of alkylolamine. Thecompounds are readily dispersible or soluble in Water, are stable inmildly acid and alkaline media, and are efiective in the presence ofcalcium and magnesium ions. They are surface-active agents, functioningas detergents, and as agents for dispersing and emulsifying solids andliquids in water.

The higher fatty acids (six or more carbon atoms) are preferred for thealiphatic radical. One such compound is Ninol 979. It is a active,nonionic, pale amber liquid with a specific gravity of 1.00,corresponding to the product of condensing lauric acid withdiethanolamine.

The properties of the Ninols change in degree as the composition varies,and with difierent ones the amounts required vary for any predeterminedextent of function. Hence, where an amount is specified in a formulaherein, the particular member of the family is specified.

Ethofats are trade-marked products of Armour and Company, ChemicalDivision, Chicago, Illinois. They are a family of fat-derived nonionicsurface-active agents. They are polyoxyethylene-glycol esters of fattyacids, having the general formula:

R-ii-owmommzn They vary from fluid liquids to soft pastes depending uponlength and saturation of the fatty chain and the relative proportion ofthe polyethylene glycol residue, which factors also control thesolubilities. As the value of x increases in a given formula, thematerial becomes more soluble in water and correspondingly less solublein nonpolar organic compounds. All of the Ethofats are water-soluble orwater-dispersible.

The Ethofats are resistant to hydrolysis and therefore, stable to mildlyacid and alkaline conditions. They are unatfected by calcium, magnesiumor other hard water ions. They are compatible with nearly all types ofsurface-active agents, and function as detergents and as dispersing andemulsifying agents.

The polyethylene glycol employed for the material may have a molecularweight from 220 to 2200, which determines the value of x in the formula.The radical R in the formula is a fatty acid radical, saturated orunsaturated, or mixed radicals of the acids caprylic, capric, lauric,myristic, palmitic, stearic, oleic, linoleic, linolenic, and rosinacids.

Ethofat 242 is one in which the radical R, taken as 100%, consists of15% of oleyl radical, 15% of linoleyl radical, and 70% of the radicalsof rosin acids.

Since the value of x in the general formula may vary and in thecommercially available Ethofats varies from 5 to 50, the constitutionand hence the solubility are indicated in the commercial identification,thus:

Ethofat 242/(x-l-10) Ethofat 242/60 is thus a mono-ester of mixedorganic acids R (as specified above) with polyoxyethylene glycoladdition having an average molecular weight of 2200, corresponding tox=50. Likewise, Ethofat 242/20 involves instead a polyoxyethylene glycolhaving an average molecular weight of 440, corresponding to x: 10.

The foregoing information is found in bulletins by the manufacturer, andin part has been abstracted from Chemical and Engineering News, vol. 27,No. 39, September 26, 1949, page 2756.

The compounds Neutronyx are a family of trademarked materials made byOnyx Oil Chemical Company, Jersey City 2, New Jersey. They are nonionicsurfaceactive agents, functioning as detergents, emulsifiers anddispersants. They vary from liquids to low-melting waxlike' solids, alldispersible in water. Being nonionic they are compatible with cationicand other nonionic compounds, such as quaternary ammonium compounds.They are stable in mildly acid and alkaline solutions.

Chemically, they are ethers, the various kinds being designatedcommercially by a number:

No. 330polyalkylether condensate of fatty acids No. 600-aromaticpolyglycol ether, and specifically alkyl phenyl ether with polyethyleneglycol No. 834polyalkyl ether condensate of fatty acids are pH Type X-303O 7. 5-10 Alkylated aryl polyether alcohol. X-lOO 100 7. 5-10 Do.

The above compounds are soluble in cold water in all proportions. Theyare compatible with both cationic and anionic active materials. Activityis not affected by hard water.

A suitable cationic wetting agent for the purpose is one sold asAlkaterge O by Commercial Solvents Corporation. It is the oxazoline fromoleic acid and 2-amino-2- methyl-1,3-pentanediol.

When wetting agent is used, any amount upwardly from zero is effective,but in the case of cationic ones not over about one part to two parts ofquaternary.

The invention is not limited to drying the sheet, although drying ispreferred for what may be termed domestic uses. It is possible toimmerse the sheets and to leave them well drained but wet, and so topackage the wet sheets in a water-proof pack, for a soldiers or acamping kit, as emergency swabs for wounds. In such use, the dry sheetsare not adequate when water to wet them is lacking. In such wet-packsheets of non-woven fabric as described, it has been found that thepresence of nonanionic wetting agent in addition to the germicidalquaternary, applied to wounds increases the germicidal action of thequaternary by action which is believed to be one of easing penetrationof the quaternary into minute spaces. A successful formula for such awet-pack sheet is as follows:

Wet-pack sheet.The following is an assay of a wetpack sheet of 45 gaugenon-woven cotton fabric, which is non-draining:

. Grams The 45 gauge sheet 3.25 ADBAC 2.13 Neutronyx 600 .50 Water 10.00

The same sheet may be dried and then immersed in a limited amount ofwater, or rewetted for application as a sterilizing swab.

The number of germicidal quaternary compounds known is vast, and a greatmany of them are available commercially as germicides and sanitizingagents. Choice of one over another may depend on many factors,especially costs. The following are but a few in addition to thosealready given.

Alkyl 6%;? 20 2HT Percent Percent Octyl..- 8 8 Deeyl.- 10 9 Dodecyl 1247 TetradecyL- l4 l8 Hexadecyl l6 8 Octadecyl 18 10 4. p-Tert.-octy1phenoxy ethoxyethyl dimethyl benzyl ammonium chloride The presentinvention therefore involves the production of sheets of controlledcharacter in combination with carried germicidal quaternary compounds,with or without non-anionic wetting agents, and preferably in driedform, except that in the case of sheets having controlled availablecapillarity as described, the sheets may be maintained wet or dry asarticles for use or in commerce.

Practically all of the carried quaternary is available and releasable towater, and that which is not, is the adsorbed substantive layer. Thereleasable quantity is substantially uniform for any given area of theprepared sheet, and from the potency of the quaternary, and the requiredusage, one may readily prescribe the maximum amount of water into whicha given size of carrying-sheet may be placed to produce a sterilizingsolution of at least the requisite strength.

In the case of ADBAC as the only agent carried by a sheet, a commonregulated standard is 200 parts per million for dairy use. The presentinvention provides in Cases A and B above, sheet materials, thedescribed sizes of which may be placed in a three-gallon pail containingabout 2% gallons of water for use on a moderate sized herd of milk cows,or in a restaurant, and elsewhere.

Because cellulosic surface tends to bind the germicidal quaternarymaterial to it, a germicidal solution of it at near the criticalconcentration is subject to depletion of germicidal content uponimmersing therein, for example, a clean cellulosic applicator, havingpower to remove germicidal content from solution and bind it to thecellulosic surface. By so doing, the power of the remaining solution isweakened. It is a great advantage of the present invention that suchdepletion is not possible with respect to the applicator-carrier sheethereof. Such sheet yields some germicide to the water, rather thantaking it from the water, and the resulting applicator has its surfacesatiated with the germicide.

It is to be understood that the invention is not limited to theproportions or the materials particularly described for the purpose ofillustrating and explaining the invention, and that numerous variationsare contemplated as falling within the scope of the appended claims.

I claim:

1. A germicide-measuring dispenser consisting in addition to any contentof water, essentially and substantially entirely of (a) awater-insoluble water-absorbent carrier sheet of material having averageuniformity of structure, the microscopic surface of the sheet beingentirely the surface of hydrophilic water-insoluble cellulosic gel, and(b) water-soluble substance consisting essentially of nonanionicsurface-active material carried in substantially uniform distributionper unit area of sheet by and on said surface, essentially includinggermicidal cationic quaternary ammonium salt only in part substantivelyattached to said surface by that character of orientation elfected inwater solution, said germicidal salt being present in quantity of atleast two-thirds of all the cationic surface-active material present,the excess of said germicidal salt over that portion of it which issubstantively held by said surface being releasable on immersion of thesheet in Water, whereby a given unit area of sheet may be immersed in apredetermined volume of water to provide a germicidal solution, and thecarrier sheet may be used as an applicator of said solution withoutreduction of the germicidal concentration.

2. A germicide-measuring dispenser consisting in addition to any contentof water, essentially and substantially entirely of (a) awater-insoluble water absorbent sheet comprising fibers fixed ingenerally side-by-side relationship and coated and bonded to sheet formin relatively fixed positions with respect to each other by thin coatsand connecting webs of regenerated cellulose, said sheet beingcharacterized over its area by substantial uniformity of distribution ofits regenerated cellulose surface and substantial uniformity ofdistribution and volume of resulting fiber-formed capillary space, and(b) Water-soluble substance consisting essentially of non-anionicsurfaceactive material carried in substantially uniform distribution perunit area of sheet by and on said surface, essentially includinggermicidal cationic quaternary ammonium salt only in part substantivelyattached to said surface by that character of orientation effected inwater solution, said germicidal salt being present in quantity of atleast two-thirds of all the cationic surface-active material present,the excess of said germicidal salt over that portion of it which issubstantively held by said surface being releasable on immersion of thesheet in water, whereby a given unit area of sheet may be immersed in apredetermined volume of Water to provide a germicidal solution, and thecarrier sheet may be used as an applicator of said solution withoutreduction of the germicidal concentration.

3. A dry sheet according to claim 2.

4. A germicide-measuring dispenser consisting in addition to any contentof water, essentially and substantially entirely of (a) awater-insoluble water absorbent sheet comprising fibers fixed ingenerally side-by-side relationship and coated and bonded to sheet formin relatively fixed positions with respect to each other by thin coatsand connecting webs of regenerated cellulose, said sheet beingcharacterized over its area by substantial uniformity of distribution ofits regenerated cellulose surface and substantial uniformity ofdistribution and volume of resulting fiber-formed capillary space, and(b) in substantially uniform distribution per unit area of sheetwater-soluble substance consisting essentially of nonionicsurface-active agent and germicidal cationic quaternary ammonium salt,the latter being only in part substantively attached to the surface ofthe regenerated cellulose by that character of orientation effected inwater solution, and the remaining part being releasable on immersion ofthe sheet in water, whereby a given unit area of sheet may be immersedin a predetermined volume of water to provide a germicidal solutioncontaining said nonionic surface-active agent, and the carrier sheet maybe used as an applicator of said solution without reduction of thegermicidal concentration.

5. A dry sheet according to claim 4.

6. In the process of forming a non-woven fabric which comprises forminga web of combed fibers, wetting said Web with a solution of dissolvedcellulose capable of treatment to regenerate cellulose, regeneratingsaid cellulose as a coating and bonding agent for said fibers in situ inthe web, and washing out the residual soluble material in theregenerated cellulose with water, the step of applying to said wetwashed sheet prior to drying an aqueous dispersion consisting of waterand non-anionic surface-active material essentially including germicidalcationic quaternary ammonium salt, said germicidal salt being present insaid solution in quantity of at least twothirds of all the cationicsurface-active content and at a heavy concentration of the order of 10%to 30% by weight of said solution, whereby to cause substantiveattachment of one portion of the cationic material of said solution tothe regenerated cellulose surface and to wet the sheet with asubstantially uniform content per unit area of said solution and therebyprovide said remainder of the germicidal cationic material as a portionreleasable into water to provide a germicidal solution on immersing agiven unit area of sheet in a predetermined quantity of water, andwhereby the immersed piece of sheet may be used as an applicator of saidsolution without reduction of the germicidal concentration.

References Cited in the file of this patent UNITED STATES PATENTS1,353,954 Henry Sept. 28, 1920 2,063,218 Zisserman Dec. 8, 19362,255,694 Beale Sept. 9, 1941 2,346,632 Wolfert Apr. 11, 1944 2,349,152Feinstone May 18, 1944 2,390,235 Barnard Dec. 4, 1945 2,436,673 SheltonFeb. 24, 1948 2,474,306 Doub June 28, 1949 2,542,909 DeWet Feb. 20, 1951FOREIGN PATENTS 236,877 Switzerland Mar. 15, 1945 23,237 SwitzerlandJan. 14, 1901 OTHER REFERENCES Hyamines; 1622 and l0-X. Rohm & Haas Co.,Philadelphia, Pa., 1947, 16 pages.

Pharmaceutical Formulas, vol. 1, The Chemist and Druggist, London, 1944,pages 45, 46.

1. A GERMICIDE-MEASURING DISPENSER CONSISTING IN ADDITION TO ANY CONTENTOF WATER, ESSENTIALLY AND SUBSTANTIALLY ENTIRELY OF (A) AWATER-INSOLUBLE WATER-ABSORBENT CARRIER SHEET OF MATERIAL HAVING AVERAGEUNIFORMITY OF STRUCTURE THE MICROSCOPIC SURFACE OF THE SHEET BEINGENTIRELY THE SURFACE OF HYDROPHILIC WATER-INSOLUBLE CELLULOSIC GEL, AND(B) WATER-SOLUBLE SUBSTANCE CONSISTING ESSENTIALLY OF NONANIONICSURFACE-ACTIVE MATERIAL CARRIED IN SUBSTANTIALLY UNIFORM DISTRIBUTIONPER UNIT AREA OF SHEET BY AND ON SAID SURFACE, ESSENTIALLY INCLUDINGGERMICIDAL CATIONIC QUATERNARY AMMONIUM SALT ONLY IN PART SUBSTANTIVELYATTACHED TO SAID SURFACE BY THAT CHARACTER OF ORIENTATION EFFECTED INWATER SOLUTION, SAID GERMICIDAL SALT BEING PRESENT IN QUAN TITY OF ATLEAST TWO-THIRDS OF ALL THE CATIONIC SURFACE-ACTIVE MATERIAL PRESENT,THE EXCESS OF SAID GERMICIDAL SALT OVER THAT PORTION OF IT WHICH ISSUBSTANTIVELY HELD BY SAID SUR FACE BEING RELEASABLE ON IMMERSION OF THESHEET IN WATER, WHEREBY A GIVEN UNIT AREA OF SHEET MAY BE IMMERSED IN APREDETERMINED VOLUME OF WATER TO PROVIDE A GERMICIDAL SOLUTION, AND THECARRIER SHEET MAY BE USED AS AN APPLICATOR OF SAID SOLUTION WITHOUTREDUCTION OF THE GERMICIDAL CONCENTRATION.